Summary of the invention
Propose a kind of technique of this waste water slag of recycling treatment herein, the metals such as nickel cobalt MnZn copper can reclaim by this technique completely, the cobalt nickel manganese solution simultaneously obtained can be used as the raw material of preparation NCM ternary precursor, avoid the separation of cobalt nickel manganese, technique is more simple, and metal recovery rate improves greatly, and cost is low, environmental sound, has the prospect of industrialization.
Concrete technology principle is as follows:
1. reducing leaching.Main component due to waste water slag is precipitate metal hydroxides, and it exposes in atmosphere and following reaction can occur:
Co(OH)
2+2H
2O+O
2=Co(OH)
3
Mn(OH)
2+O
2=MnO
2+2H
2O
Leach so need add after trivalent cobalt and tetravalent manganese are reduced into divalence by reductive agent, for S-WAT, the chemical equation that reducing leaching occurs is as follows:
2Co(OH)
3+2H
2SO
4+Na
2SO
3=2CoSO
4+5H
2O+Na
2SO
4
MnO
2+2H
2SO
4+Na
2SO
3=MnSO
4+H
2O+Na
2SO
4
2Fe(OH)
3+2H
2SO
4+Na
2SO
3=2FeSO
4+5H
2O+Na
2SO
4
2M(OH)
3+2H
2SO
4=2M
2(SO
4)
3+6H
2O
(M be Al, Cr etc. three valence state metal)
M(OH)
2+H
2SO
4=MSO
4+H
2O
(M is the divalent state metals such as Zn, Cu, Ni, Ca, Mg)
Solution after dissolving is the metal ion such as deironing aluminium chromium again, and for sodium chlorate and sodium hydroxide, the chemical equation that deironing aluminium chromium etc. occur is as follows:
6FeSO
4+12NaOH+NaClO
3+3H
2O=NaCl+6Fe(OH)
3+6Na
2SO
4
M
2(SO
4)
3+ 6NaOH=2M (OH)
3+ 3Na
2sO
4(M be Al, Cr etc. three valence state metal)
2. manganese powder displacement.Because the lively type of manganese is higher than copper, so manganese powder can copper in substitutional solution, its chemical equation occurred is as follows:
Mn+CuSO
4=Cu+MnSO
4
3. manganese sulfide dezincifies.Because the solubleness of zinc sulphide is far below manganese sulfide, therefore can remove zine ion with manganese sulfide, the chemical equation of its reaction is as follows:
MnS+ZnSO4=MnSO4+ZnS
4. Sodium Fluoride calcium-magnesium removing.Because the solubleness of Calcium Fluoride (Fluorspan), magnesium fluoride is less, therefore available fluoride carrys out removal of impurities, and for Sodium Fluoride, the chemical equation of its reaction is as follows:
CaSO
4+2NaF=CaF
2+Na
2SO
4
MgSO
4+2NaF=MgF
2+Na
2SO
4
5.P204 extracting and enriching.P204 extraction agent by the metal ion in the aqueous solution as cobalt nickel mn ion is extracted in organic phase from water, then can control comparing of back extraction, thus obtains the nickel cobalt manganese solution of high density, and sodium ion etc. stay in aqueous.
6. the manganese sulfide degree of depth dezincifies.Because P204 also by enrichments such as zinc-coppers, can cause the content of zinc and copper in strip liquor higher, do nickel-cobalt-manganternary ternary anode material higher for impurity element requirements such as zinc-coppers, so manganese sulfide deep impurity-removing need be used again.
Compare conventional sulfide precipitation-roasting method process waste water slag, decrease the discharge of the sulfurous gass such as sulfurous gas, simultaneously energy synthetical recovery various metals, technical process is short, and equipment is simple, and metal recovery rate is high, and cost is low.
The technical solution used in the present invention is as follows:
A kind of cobalt metallurgy of nickel waste water slag recycling processing method, is characterized in that: comprise following step:
1) reducing leaching.According to solid-to-liquid ratio 1:2-6 by waste water slag pulp, add the pH1-2 that acid maintains reaction, add reductive agent according to cobalt manganese mol ratio 1:0.5-4 simultaneously, stirring reaction 1-3 hour at 50-70 DEG C, oxygenant is added according to iron mol ratio 1:0.1-0.6, add the pH3.5-5.5 of alkali regulator solution, stir after 1-4 hour and filter;
2) manganese powder displacement copper.Filtrate after removal of impurities is added acid for adjusting pH 1-3, adds manganese powder according to copper mol ratio 1:1.05-1.5, maintain temperature of reaction 40-80 DEG C, stirring reaction 1-3 hour;
3) manganese sulfide dezincifies.Filtrate after copper removal is added acid and maintain reaction pH1-3, add manganese sulfide according to zinc mol ratio 1:1.1-1.5, temperature of reaction 40-80 DEG C, react after 1-3 hour and filter;
4) fluorochemical calcium-magnesium removing.Solution after dezincifying alkaline solution maintains the pH3-6.5 of solution, adds fluorochemical, maintain filtration in temperature of reaction 50-90 DEG C, stirring reaction 1-3 hour according to calcium magnesium mol ratio 1:1.2-2.0;
5) P
20
4extracting and enriching.Get P
20
4extraction agent (10-30%P204+70-90% sulfonated kerosene), use alkaline solution saponification, saponification degree 50-75%, with the extraction of separating funnel simulation 6-9 stage countercurrent, the washing of 4-6 stage countercurrent, the back extraction of 8-10 stage countercurrent, charging pH3.5-5.5, wash the sulfuric acid of acid for 0.5mol/l, sour regurgitation is the sulfuric acid of 2mol/l, feed liquid: P204: wash acid: sour regurgitation=1:4-8:0.1-0.3:0.4-0.8(volume flow ratio);
6) the manganese sulfide degree of depth dezincifies.By P
20
4filtrate after enrichment adds sulfuric acid and maintains reaction pH 1-3, adds manganese sulfide, temperature of reaction 50 DEG C, react after 1-3 hour and filter according to zinc-copper mol ratio 1:5.
In described step 1, acid is at least one in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, reductive agent is at least one in sulfurous acid, sulphite, oxygenant is at least one in hydrogen peroxide, oxymuriate, oxygen, and alkali is at least one in sodium hydroxide, potassium hydroxide, hydrated barta, ammoniacal liquor;
In described step 2, acid is at least one in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid;
In described step 3, acid is at least one in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid;
In described step 4, alkali is at least one in sodium hydroxide, potassium hydroxide, hydrated barta, ammoniacal liquor, and fluorochemical is at least one in Potassium monofluoride, Sodium Fluoride, Neutral ammonium fluoride, hydrogen fluoride;
In described step 5, alkali is at least one in sodium hydroxide, potassium hydroxide, hydrated barta, ammoniacal liquor.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows:
1. the metals such as nickel cobalt MnZn copper can reclaim by this technique completely, and the slag as deironing aluminium can be used as cement raw material, thus has reclaimed the metallic elements such as iron aluminium wherein.Manganese powder displacement obtains copper powder thus has reclaimed copper wherein, and the manganese sulfide sulfuration cadmia obtained that dezincifies is higher-grade zinc raw material thus has reclaimed zinc wherein, and the ternary liquid finally obtained has reclaimed nickel Co-Mn metal element wherein.
2. it is LiNixCoyMn (1-x-y) O2(NCM that the cobalt nickel manganese solution obtained can be used as preparation) the raw material of ternary precursor, avoid the separation of cobalt nickel manganese, technique is more simple, and metal recovery rate improves greatly.
Cost is low, environmental sound, does not substantially produce castaway slag, has the prospect of industrialization.
Embodiment
Following table is waste water slag composition
Waste water slag composition %
Co |
Ni |
Cu |
Mn |
Zn |
Ca |
Mg |
Fe |
Al |
Cr |
Na |
1.0 |
3.5 |
1.8 |
9.5 |
4.8 |
6.9 |
4.2 |
0.4 |
0.3 |
0.1 |
20.1 |
Cd |
Pb |
|
|
|
|
|
|
|
|
|
0.02 |
0.01 |
|
|
|
|
|
|
|
|
|
According to solid-to-liquid ratio 1:3 by waste water slag pulp, add the pH1.5 that sulfuric acid maintains reaction, add S-WAT according to cobalt manganese mol ratio 1:1 simultaneously, stirring reaction 1.5 hours at 70 DEG C, solution after dissolving is the metal ion such as deironing aluminium chromium again, adds sodium chlorate and adds sodium tetraphenylborate according to iron mol ratio 1:0.02, add about the pH4.0 of liquid caustic soda regulator solution according to iron mol ratio 1:0.3, stir after 1.5 hours and filter, after deironing, liquid composition is as following table.
Liquid composition g/l after deironing
Co |
Ni |
Mn |
Cu |
Zn |
Mg |
Na |
Ca |
Other |
3.3 |
10.1 |
28.5 |
5.4 |
14.9 |
13.8 |
65 |
0.6 |
≦0.01 |
Filtrate after removal of impurities is added sulfuric acid and regulate pH2.0, add 100 object manganese powders and the Tetramethylammonium hydroxide according to copper mol ratio 1:0.2 according to copper mol ratio 1:1.1, maintain temperature of reaction 60 DEG C, stirring reaction 2 hours, filter, copper powder composition is as following table.
Copper powder composition %
Cu |
Mn |
Ni |
Co |
Zn |
95.6 |
3.5 |
0.1 |
0.11 |
0.05 |
Filtrate after copper removal is added sulfuric acid and maintain reaction about pH1.5, add manganese sulfide, temperature of reaction 50 DEG C according to zinc mol ratio 1:1.2, react after 2 hours and filter, after dezincifying, liquid and dezincification slag ingredient are as following table.
Liquid composition g/l after dezincifying
Co |
Ni |
Mn |
Cu |
Zn |
Mg |
Na |
Ca |
Other |
3.1 |
9.8 |
50.1 |
0.0015 |
0.005 |
13.7 |
66 |
0.6 |
≦0.01 |
Dezincification slag ingredient %
Zn |
Mn |
Ni |
Cu |
Co |
50.1 |
10.1 |
0.2 |
0.3 |
0.6 |
Solution after dezincifying liquid caustic soda maintains about the pH4.0 of solution, adds Sodium Fluoride according to calcium magnesium mol ratio 1:1.5, maintains temperature of reaction 85 DEG C, and stirring reaction filters for 2 hours, filtrate and filter residue composition as follows.
Liquid composition g/l after calcium-magnesium removing
Co |
Ni |
Mn |
Cu |
Zn |
Mg |
Na |
Ca |
Other |
3.1 |
9.7 |
50.0 |
0.0015 |
0.005 |
0.003 |
85 |
0.002 |
≦0.01 |
Filter residue analytical results %
Ca |
Mg |
Ni |
Mn |
Co |
Zn |
7.2 |
35.1 |
0.01 |
0.3 |
0.01 |
0.01 |
Get P204 extraction agent (20%P204+80% sulfonated kerosene), use liquid caustic soda saponification, saponification degree 60%, 8 stage countercurrent extractions, 4 stage countercurrent washings, 8 stage countercurrent back extractions are simulated with separating funnel, charging pH4.0, wash the sulfuric acid of acid for 0.5mol/l, sour regurgitation is the sulfuric acid of 2mol/l, feed liquid: P204: wash acid: sour regurgitation=1:5:0.15:0.6(volume flow ratio), the strip liquor finally obtained and raffinate analytical results are as following table.
Strip liquor composition g/l
Co |
Ni |
Mn |
Cu |
Zn |
Mg |
Na |
Ca |
Other |
5.3 |
16.5 |
79.5 |
0.0025 |
0.008 |
0.005 |
0.002 |
0.005 |
≦0.002 |
Raffinate ingredient m g/l
Co |
Ni |
Mn |
Cu |
Zn |
1.2 |
2.1 |
0.2 |
0.2 |
0.1 |
Filtrate after P204 enrichment is added sulfuric acid and maintain reaction about pH2.0, add manganese sulfide, temperature of reaction 50 DEG C according to zinc-copper mol ratio 1:5, react after 2 hours and filter, the filtrate obtained is as following table.
Ternary liquid g/l after the degree of depth dezincifies
Co |
Ni |
Mn |
Cu |
Zn |
Mg |
Na |
Ca |
Other |
5.2 |
16.3 |
79.5 |
0.0012 |
0.003 |
0.005 |
0.002 |
0.005 |
≦0.002 |
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.